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CO and CLO
CHAPTER 4:
THERMODYNAMICS AND EQUILIBRIA Course outcome (CO)
CO3: Evaluate the concept of redox reaction,
thermochemistry and kinetic reactions in chemical
First Law of Thermodynamics engineering.

Second Law of Thermodynamics Course Learning Outcome (CLO)

1. State and use the first and second laws of
Physical Transformations of Pure Substances thermodynamics.
2. Calculate Gibbs and Helmholtz energies.
Simple Mixtures
3. Apply thermodynamics concepts to explain the
properties of solutions.
Chemical Equilibria
4. Explain single and two-component phase diagrams.
5. Apply thermodynamics concepts to explain
spontaneity, chemical and electrochemical equilibria.

Spontaneous Processes
Second Law of
Thermodynamics Thermodynamics is concerned with the question: can a
reaction occur?
First Law of Thermodynamics: energy is conserved.
Any process that occurs without outside intervention is
spontaneous.
(Chapter 19: Chemical Thermodynamics) When two eggs are dropped they spontaneously break.
The reverse reaction is not spontaneous.
We can conclude that a spontaneous process has a
direction.

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Spontaneous Processes Spontaneous Processes

A process that is spontaneous in one direction is not

spontaneous in the opposite direction.
The direction of a spontaneous process can depend on
temperature: Ice turning to water is spontaneous at T >
0C, Water turning to ice is spontaneous at T < 0C.

Prentice Hall 2003 Chapter 19 Prentice Hall 2003 Chapter 19

Spontaneous Processes
Reversible and Irreversible Processes
When 1 mol of water is frozen at 1 atm at 0C to form 1
mol of ice, q = Hvap of heat is removed.
To reverse the process, q = Hvap must be added to the
1 mol of ice at 0C and 1 atm to form 1 mol of water.
Therefore, converting between 1 mol of ice and 1 mol
of water at 0C is a reversible process.
Allowing 1 mol of ice to warm is an irreversible process.
To get the reverse process to occur, the water
temperature must be lowered to 0C.

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Reversible and Irreversible Processes Reversible and Irreversible Processes

Irreversible process
A reversible process is one that can go back and forth
between states along the same path.
heat flow between two objects that have almost
similar temperature can be reversed by having
infinitesimal change in temperature.
A irreversible process is one that cannot simply be
reversed to restore the system and its surroundings to
their original states.
Heat can not flow from the colder object to the hotter
one.

Prentice Hall 2003 Chapter 19 Prentice Hall 2003 Chapter 19

Reversible and Irreversible Processes The Spontaneous Expansion of a Gas

Chemical systems in equilibrium are reversible.
In any spontaneous process, the path between
reactants and products is irreversible.
Thermodynamics gives us the direction of a
process. It cannot predict the speed at which the
process will occur.
Consider an initial state: two flasks connected by a
closed stopcock. One flask is evacuated and the other
contains 1 atm of gas.
The final state: two flasks connected by an open
stopcock. Each flask contains gas at 0.5 atm.
The expansion of the gas is isothermal (i.e. constant
temperature). Therefore the gas does no work and
heat is not transferred.

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The Spontaneous The Spontaneous Expansion of a Gas

Expansion of a Gas
Consider the simple case where there are two gas
molecules in the flasks.
Before the stopcock is open, both gas molecules will be
The Spontaneous in one flask.
Expansion of a Gas Once the stopcock is open, there is a higher probability
that one molecule will be in each flask then both
molecules being in the same flask.

Prentice Hall 2003 Chapter 19

The Spontaneous Expansion of a Gas Second Law of Thermodynamics

When there are many molecules, it is much more
probable that the molecules will distribute among to the
two flasks than all remain in only one flask.
Any irreversible process results in an
overall increase in entropy, whereas a
reversible process results in no overall
change in entropy

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Entropy and the Second Law Entropy and the Second Law
of Thermodynamics of Thermodynamics
Entropy Entropy
Entropy, S, is a measure of the disorder of a system. As ice melts, the intermolecular forces are broken
Spontaneous reactions proceed to lower energy or (requires energy), but the order is interrupted (so
higher entropy. entropy increases).
In ice, the molecules are very well ordered because of Water is more random than ice, so ice spontaneously
the H-bonds. melts at room temperature.
Therefore, ice has a low entropy.

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Entropy and the Second Law

of Thermodynamics
Entropy
There is a balance between energy and entropy
considerations.
When an ionic solid is placed in water two things
happen:
the water organizes into hydrates about the ions (so
the entropy decreases), and
the ions in the crystal dissociate (the hydrated ions
are less ordered than the crystal, so the entropy
increases).

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Entropy Entropy and the Second Law

of Thermodynamics
Entropy
Generally, when an increase in entropy in one process
is associated with a decrease in entropy in another, the
increase in entropy dominates.
Entropy is a state function.
For a system, S = Sfinal - Sinitial.
If S > 0 the randomness increases, if S < 0 the order
increases.

Prentice Hall 2003 Chapter 19

Entropy and the Second Law Entropy and the Second Law
of Thermodynamics of Thermodynamics
.
Entropy The Second Law of Thermodynamics
Suppose a system changes reversibly between state 1 and The second law of thermodynamics explains why
state 2. Then, the change in entropy is given by spontaneous processes have a direction.
q In any spontaneous process, the entropy of the
Ssys rev (constant T ) universe increases.
T
at constant T where qrev is the amount of heat added Suniv. S syst . S surr.
reversibly to the system. (Example: a phase change the change in entropy of the universe is the sum of the
occurs at constant T with the reversible addition of heat.) change in entropy of the system and the change in
entropy of the surroundings.
Entropy is not conserved: Suniv is increasing

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Entropy and the Second Law

of Thermodynamics
The Second Law of Thermodynamics
For a reversible process: Suniv. S syst . S surr. 0
For a irreversible process: Suniv. S syst . S surr. 0
Note: the second law states that the entropy of the
universe must increase in a spontaneous process. It is
possible for the entropy of a system to decrease as
long as the entropy of the surroundings increases.
For an isolated system, Ssys = 0 for a reversible
process and Ssys > 0 for a spontaneous process.

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The Molecular Interpretation of Entropy

A gas is less ordered than a liquid that is less ordered

than a solid.
Any process that increases the number of gas
molecules leads to an increase in entropy.
When NO(g) reacts with O2(g) to form NO2(g), the total
number of gas molecules decreases, and the entropy
decreases.

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The Molecular Interpretation of The Molecular Interpretation of

Entropy
There are three atomic modes of motion:
translation (the moving of a molecule from one point in
space to another),
vibration (the shortening and lengthening of bonds,
including the change in bond angles),
rotation (the spinning of a molecule about some axis).
Entropy
Energy is required to get a molecule to translate,
vibrate or rotate.
The more energy stored in translation, vibration and
rotation, the greater the degrees of freedom and the
higher the entropy.
In a perfect crystal at 0 K there is no translation,
rotation or vibration of molecules. Therefore, this is a
state of perfect order.

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The Molecular Interpretation of The Molecular Interpretation of

Entropy Entropy
Third Law of Thermodynamics: the entropy of a perfect
crystal at 0 K is zero.
Entropy changes dramatically at a phase change.
As we heat a substance from absolute zero, the
entropy must increase.
If there are two different solid state forms of a
substance, then the entropy increases at the solid state
phase change.

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The Molecular Interpretation of

Entropy
Boiling corresponds to a much greater change in
entropy than melting.
Entropy will increase when
liquids or solutions are formed from solids,
gases are formed from solids or liquids,
the number of gas molecules increase,
the temperature is increased.

Prentice Hall 2003 Chapter 19

Entropy Changes in Chemical

Reactions
Absolute entropy can be determined from complicated
measurements.
Standard molar entropy, S: entropy of a substance in its
standard state. Similar in concept to H.
Units: J/mol-K. Note units of H: kJ/mol.
Standard molar entropies of elements are not zero.
For a chemical reaction which produces n moles of
products from m moles of reactants:
S nS products mS reactants

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Gibbs Free Energy

For a spontaneous reaction the entropy of the universe
must increase.
Reactions with large negative H values are
spontaneous.
How to we balance S and H to predict whether a
reaction is spontaneous?
Gibbs free energy, G, of a state is
G H TS
For a process occurring at constant temperature
G H TS

Prentice Hall 2003 Chapter 19 Prentice Hall 2003 Chapter 19

Gibbs Free Energy Gibbs Free Energy

There are three important conditions:

If G < 0 then the forward reaction is spontaneous.
If G = 0 then reaction is at equilibrium and no net
reaction will occur.
If G > 0 then the forward reaction is not
spontaneous. If G > 0, work must be supplied
from the surroundings to drive the reaction.
For a reaction the free energy of the reactants
decreases to a minimum (equilibrium) and then
increases to the free energy of the products.

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Gibbs Free Energy

Consider the formation of ammonia from nitrogen and
hydrogen:
N2(g) + 3H2(g) 2NH3(g)
Initially ammonia will be produced spontaneously (Q <
Keq).
After some time, the ammonia will spontaneously react
to form N2 and H2 (Q > Keq).
At equilibrium, G = 0 and Q = Keq.

Prentice Hall 2003 Chapter 19 Prentice Hall 2003 Chapter 19

Gibbs Free Energy

Standard Free-Energy Changes
We can tabulate standard free-energies of formation, Gf
(c.f. standard enthalpies of formation).
Standard states are: pure solid, pure liquid, 1 atm (gas), 1
M concentration (solution), and G = 0 for elements.
G for a process is given by
G nG f products mG f reactants
The quantity G for a reaction tells us whether a mixture
of substances will spontaneously react to produce more
reactants (G > 0) or products (G < 0).

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Free Energy and Temperature Free Energy and Temperature

Focus on G = H - TS:
If H < 0 and S > 0, then G is always negative.
If H > 0 and S < 0, then G is always positive. (That is,
the reverse of 1.)
If H < 0 and S < 0, then G is negative at low
temperatures.
If H > 0 and S > 0, then G is negative at high
temperatures.
Even though a reaction has a negative G it may occur too
slowly to be observed.

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Free Energy and The Free Energy and The

Equilibrium Constant Equilibrium Constant
Recall that G and K (equilibrium constant) apply to At equilibrium, Q = K and G = 0, so
standard conditions. G G RT ln Q
Recall that G and Q (equilibrium quotient) apply to any
conditions. 0 G RT ln Keq
It is useful to determine whether substances under any G RT ln Keq
conditions will react:
From the above we can conclude:
If G < 0, then K > 1.
G G RT ln Q If G = 0, then K = 1.
If G > 0, then K < 1.

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